Fabrication of hierarchical composite microspheres of copper-doped Fe3O4@P4VP@ZIF-8 and their application in aerobic oxidation
Fabrication of hierarchical composite microspheres of copper-doped Fe3O4@P4VP@ZIF-8 and their application in aerobic oxidation
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DOI：
10.1039/c6nj02239a
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发表时间：
2016-11
影响因子：
3.3
通讯作者：
Junying Hou;Y. Luan;Jie Yu;Y. Qi;Ge Wang;Yunfeng Lu
中科院分区：
文献类型：
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作者：
Junying Hou;Y. Luan;Jie Yu;Y. Qi;Ge Wang;Yunfeng Lu
成功地制备了新型的铜掺杂Fe3O4@poly(4-vinylpyridine-co-divinylbenzene)@ZIF-8层状磁性复合微球。首次采用聚合法制备了Fe3O4(PAA)@P4VP磁性微球，其中4-乙烯基吡啶(4-VP)单体通过氢键作用与聚丙烯酸改性的Fe3O4的α-COOH基团相互作用。然后，锌离子被吸附到P4VP壳的表面，然后与2-甲基咪唑形成ZIF-8多孔壳。最后，将近5.45wt%的铜含量引入到ZIF-8骨架中，形成了磁性核壳结构的铜掺杂Fe3O4@P4VP@ZIF-8。将制得的掺铜Fe3O4@P4VP@ZIF-8催化剂用于醇的选择氧化和以分子氧为氧化剂的烯烃环氧化反应。结果表明，磁性核壳掺铜催化剂Fe3O4@P4VP@ZIF-8具有较好的催化活性，与其他铜MOF催化剂相比，其催化活性显著提高(最高可达8.25h−1)。此外，这种多相催化剂可以循环至少15次而不会有明显的活性损失。
Novel hierarchical magnetic composite microspheres of copper-doped Fe3O4@poly(4-vinylpyridine-co-divinylbenzene)@ZIF-8 (Cu-FPZ, Cu stands for copper doped) were successfully fabricated. The core–shell Fe3O4(PAA)@P4VP magnetic microspheres were first synthesized by a polymerization approach, in which the 4-vinylpyridine (4-VP) monomer interacted with a –COOH group of poly(acrylic acid) modified Fe3O4 by means of a hydrogen-bond interaction. Then Zn2+ was adsorbed on the surface of the P4VP shell, followed by the formation of a ZIF-8 porous shell with 2-methylimidazolate. Finally, nearly 5.45 wt% of copper content was incorporated with the ZIF-8 framework to form a magnetic core–shell copper-doped Fe3O4@P4VP@ZIF-8. The obtained copper-doped Fe3O4@P4VP@ZIF-8 catalyst was applied in the selective oxidation of alcohols and epoxidation of olefins using molecular oxygen as the oxidant. The results demonstrated that the magnetic core–shell copper-doped Fe3O4@P4VP@ZIF-8 catalyst showed better catalytic activity with significantly improved turnover number and turnover frequency (up to 8.25 h−1) than other copper MOFs. Furthermore, this heterogeneous catalyst could be cycled at least 15 times without significant loss of activity.